Manufacture of halogenated alcohols



United States Patent 3,189,656 MANUFACTURE 9F HALOGEJATED ALCGHSLSJoseph Gordon and Cyril Woolf, Morristown, N.J., as-

signors to Aiiied Chemical Corporatien, New York, N. a corporation ofNew York No Drawing. Fiied Get. 4, 1961, Ser. No. 142,784 4 Claims. (Ci.260-633) This invention is directed tosym-tetrafluorodichloroisopropanol, CClF .C-H(OH).CClF and its one waterbydra-te, CCIF .CH(OH).CCIF .H O, and to processes for making the same.

Objects of the invention are to provide the foregoing new products, andto afford commercially feasible, easily controllable methods foreffecting reduction of .perhalogenated ketones by elemental hydrogen toform certain fluorochloroalcohols.

According to the invention, it has been found that whensym-tetrafiuorodichloroacetone, CClP .CO.CClF is subjected to the actionof hydrogen in the presence of a particular catalyst, and atsuperatmospheric pressure, and under other herein described reactionconditions, the above indicated sought-for products may be obtained ingood yields, halogen release from the organic starting material isminimized, and catalyst poisoning correspondingly reduced.

Sym-tetrafluorodichloroacetone at ordinary conditions is a substantiallycolorless liquid of the composition COlF .CO.CClF and having boilingpoint of about 44 C. This compound may be made for example by effectingreaction between anhydrous HF and hexachloroacetone at moderatelyelevated temperature while in the presence of antimony pentahalide, andwhile maintaining the reaction mass substantially in the liquid phase,and thereafter recovering the CCl-F .CO.-CCl-F from the reactionproducts by suitable procedure such as distillation. U.S.P. 2,741,634 ofApril 10, 1956 discloses suitable procedure for makingsym-tetrafluorodichloroacetone, cc1F,.co.cc1F,.

Practice of the present invention comprises a liquid phase reactioninvolving subjectingCClF COCClF to the action of hydrogen at relativelylow temperatures and in the presence of a relatively small amount of acertain platinum catalyst and at moderately low super-atmosphericpressures. Quantities of hydrogen and catalyst, and temperature andpressure and reaction time are conjunctively chosen so that each may behigh enough to efieot substantial reaction of CC'1F2.CO.CCLF2 to formCCl'F .CH(.OH).CClF and/or the hydrate. Reaction appears to proceedalong the lines of The invention process includes procedure in which thestarting materials and the products formed, i.e. all materials in thereaction zone except the hydrogen, are maintained substantially in theliquid phase. Apparatus employed may be a simply constructed andoperated autoclave, made for example of stainless steel, nickel orMonel, and provided with an opening adapted for charging startingmaterial and discharging reaction product, agitation or shakingfacilities, a valve-controlled gas vent, and suitable hydrogen underpressure storage, pipe and valve arrangements adapted to facilitate,during progress of the entire reaction, feed of hydrogen gas undersuperatmospheric pressure to the interior of the autoclave and maintaintherein the desired pressure.

Operating factors involved in practice of the invention include aparticular catalyst, and concentration of the catalyst on the basis ofthe weight of the CC'lF .CO.CClF starting material charged to theprocess, superatmospheric pressures and degrees thereof; temperatures;and reaction time.

The catalyst employed is the known so-called Adams platinum catalyst.This catalyst and methods for making the same are described in detail onpages 463-470 of Organic Synthesis, Collected Vol. I by Gilman andHarris, John Wiley 8: Sons, Inc, New York, 1946. Briefly, the catalystis made by fusion of sodium nitrate and chloroplatinic acid. Thecatalyst before use is a brown, heavy granular material considered to beP-tO H O (platinic oxide). In the more usual practice, and as ispreferred herein, at the outset of a reaction, the catalyst is initiallycharged in the PtO .H O form indicated. During reaction in the presenceof hydrogen the material becomes more or less converted to platinumblack, i.e. metallic platinum. Accordingly, the active material isreferred to as a platinum oxide-platinum black catalyst. After extendeduse, the catalyst may be reactivated or reconstituted as described inthe publication.

The reactions of the invention are carried out preferably in thepresence of a relatively low concentration of catalyst. Moreparticularly, catalyst concentration, which is based on the weight ofthe CClF .CO.OClF charged, may lie in the range of 0.255.0% by weight.High concentrations afiord no marked yield increases, and preferablycatalyst concentration is substantially in the range of 0.5 3%, and inmore usual practice is of the order of one to 2%.

Successful practice of the invention process requires use ofsuperat-mospheric pressure which may be utilized at any value which, inconjunction with other operating factors, is at least high enough tomaintain the reaction mass (except hydrogen) in liquid phase and toeflect substantial reaction of the CClF .CO.CClF organic startingmaterial and hydrogen to form the sought-for products. Pres sures maylie substantially in the range of 30-250 lbs. per square inch gauge, butare preferably in the range of 60- 150 lbs. While maximum pressures donot appear to be particularly critical, pressures above about 15.0 lbs.pe square inch gauge do not appear to serve any worthwhile purposes. Thepreferred minimum pressure of about 60 lbs. is somewhat associated withtemperatures as below noted. 'It will be understood that pres-sure inthe reaction zone is maintained by the pressure at which hydrogen issupplied thereto, duration of hydrogen feed being suflicient to satisfythe hydrogen requirements of the particular reaction at hand, end pointof which is indicated by cessation of hydrogen utilization.

Temperatures may be those which, in conjunction with other operatingfactors, are high enough to effect substantial reaction ofCCIF2-CO.CC1F2 and hydrogen. Maximum temperature in the reaction zone ispreferably not more than C., to enhance yields and to facilitateprevention of decomposition of sought-for products. Reaction proceedssignificantly at temperatures which may be as low as 10 C. An operatingadvantage provided by the invention is that the reaction may be carriedout, with adequately good conversions and yields, at about roomtemperature (20 C.) or a little higher. The organic starting materialmay be charged to the autoclave at room temperature, and on introductionof hydrogen under pressure, reaction proceeds without application ofextraneous heat. Reaction is mildly exothermic, and during for examplethe first third or quarter of reaction time of a given batch,temperature may rise from say 5 to 15 C.

As noted, the CCIF .CO.CCIF organic starting ma terial has a boilingpoint of about 44 C. at atmospheric pressure. It has been found thatreaction proceeds in the best manner, with regard to conversions andyields, where operating temperatures and pressures are such as tomaintain substantially all the material in the redetermination of HClformed during the reaction.

actor, i.e. the organic starting material and the conversion productsformed, substantially in the liquid phase. The

inherent substantially ambient temperature characteristics of thereaction facilitate maintenance of all materials in the reaction'zoneexcept hydrogen in the liqu d phase. Particularly "when extraneous heatis not supplied, temperatures in the reactor do not inherently exceedabout 40 C. which is belowthe 44 C. atmospheric pressure boiling pointof the organic starting material. Products of the invention arecolorless liquids boiling substantially in the range of 103-112 C., andhence reaction zone temperatures should be not in excess of 100 C. asstated. With the preferred 60 lbs. minimum pressure value, even if it isdesired to hasten reaction by application of external heat, conjunctiverelation of pressure not less than about 60 lbs. and maximum temperatureof about 100 C. provides maintenance of all materials in the reactor,other than hydrogen, substantially in the liquid phase as preferred forbest practice. 7 Hence, it will be understood that in the preferredembodiments,

temperatures are'ambient temperatures, and temperatures and pressuresare correlated so as to maintain the organic starting material and theconversion products in the reactor substantially in the liquid phase.

As will be observed from the above, catalyst concentrations, pressuresand temperatures are substantially variablef Hence, variations of thesefeatures jointly and severally affect reaction time, conversion andyield. Ac-

cordingly, reaction time is widely variable, and may be anything fromsay one to 24 hours, and is finally dependent upon the nature of theother variables. Keeping in mind forexample, that within the limitsdescribed herein, increase in catalyst concentration, temperature, andpressure, and reaction time increase rate and extent of reaction,selection of optimum operating conditions with regard to all variablesinvolved may be determined by test runs. Termination'of a given reactionmay be determined by cessation of hydrogen utilization.

At the end of reaction the autoclave may be vented 'thru a Dry-Ice trayto catch any vaporized starting ma- 'terial and reaction products, andthe gaseous exit of the trap may be passed thru a water scrubber tofacilitate After venting, the contents of the reaction zone may befiltered to separate out solid catalyst. The resulting crude filteredautoclave product comprises principally sought-for products and anyunreacted CClF .CO.CClF and contains no significant amount of othercompounds. This crude material is a colorles liquid having boiling pointin the range of about 45 C. up to a little above about ---112 C.

In accordance with'the invention, it has been found that the processdescribed results in production of substantially anhydrous CClF.CH(OI-I).CClF a colorless liquid boiling at about l111 12 C., and theCClF .CH(OH).CClF .one H2O hydrate, a colorless liquid boiling at about104106 C. The indicated products may be recovered from the crudeautoclave product by distillation. 'Thus, the autoclave product may bedistilled at substantially atmospheric pressure under conditions to takeoff a forerun boiling substantially in the range of e.g. 45 C. up to103104 C. This forerun comprises unreacted starting material andpossibly asmall amount of the alcohol hydrate.

Distillation may then be continued to recover as condensate, and as aproduct of the invention, a fraction boiling substantially in the rangeof 103104 C. up to about 1l2-1l3 C. This fraction constitutes a mixtureof CClF .CH(OI-I).CClF and its indicated hydrate, these materials beingpresent in approximately equal proportions. If separate recovery of the.hydrate is desired, distillation of the 103 l04 C. to ll2 -ll3 C.fraction may be efiected accordingly.

It has been found that all of the CClF .CH(OH).CClF

. 4, constituent of the above 103-l04 C. to 1.121l3 C. fraction may berecovered as substantially anhydrous CClF .CH(OI-I).CClF by redistillingsuch fraction in the presence of a suitable dehydrating agent. Forexample, 96% sulfuric acid may be added directly to. the fraction beforedistillation, quantity of acid being by volume about half that of thehydrate contentrof the hydrate. On distillation of the liquor to whichthe dehydrating agent has been added, there is recovered a fractionhaving the approximate boiling point of 111- 112 C. which is theanhydrous.CClF .CH(OH).CClF

product, and which consists of the entire CClF .CH (OH) .CClF

constituent of the fraction.

In the following examples, unless otherwise indicated,

parts are by weight. Conversion is intended to indicate the percent byweight of organic starting material which reacted, and yield indicatespercent by weight of reacted starting material which is changed tosought-for products.

Pressures indicated are in terms of pounds per square inch gauge.

Example 1.Catalyst employed was the so-called Adams catalyst which wasmade substantially as described on pages 463 and 464 in the above notedpublication. Briefly, 70 parts of a 5% platinic chloride solutionandparts of NaNO;; were fused at about 530-540 C.

After about 30 minutes of heating, the mass was' cooled and water wasadded to Wash out soluble salts. About 1.5 parts of brown solid catalystmaterial was obtained, and in the following run the catalyst asinitially charged to the reaction was in the form of PtO .H O. l00partsof sym-tetrafluorodichloroacetone, CClF .CO.CClF and one part of thecatalyst were'charged into a steel auto,- clave at about roomtemperature. Over'a period of about 8 hours, during which time thereactor was shaken continuously, hydrogen was continuously fed into thereactor under conditions to maintain therein a pressure in the range ofabout 80-100 lbs. During about the first two hours, temperature in thereactor rose about 10 C.

-After about eight hours of total reaction time, the autoclave wasvented through a Dry Ice-acetone cooled trap, non-condensed gases werescrubbed with water, and no low boilers were observed. The scrub watercontained only traces of chloride ion. The liquor in the autoclave wasfiltered to separate catalyst, and 93 parts of crudeautoclave'd productwere obtained. This crude'material was distilled at substantiallyatmospheric pressure, and

after removal of a forerun ofa'bout'10.5 parts boiling up to about 104C., there were obtained about 77 parts of condensate boilingsubstantially in the range of 104-" 112 C., and about 6 parts of stillresidue boiling above about 112 C. The l04-112 C. fractionincludedabout' 24 parts boiling substantially in the range of 104-106C., and about 29parts boiling substantially in the range 015111-112 C.Conversion was about 89.5%. 7 Analysis work, including infraredspectrograms, which showed the presence of alcohol and hydrate groupingsand the disappearance of the keto group, demonstrated that the 77 partsof material boiling substantially, in the range of 1041 12. C. was amixture of sym tetrafluorodichloro- -1sopropanol, CClF .CH(OI-I).CClFand its one water hydrate, CClF .CH(OH).CClF .H O. Yield of the mixtureof the isopropanol and its hydrate was about 86%? The 77 parts of theisopropanol and its hydrate mixture .were redistilled in the presenceof' parts of 96% strength sulfuric acid. are hydrate was converted tothe anhydrous material, and there were obtained as 'condensate aboutparts of a colorless liquid with a pungent'odor, boiling in the range ofabout Ill-112 C which material was identifiedby analysis means above.

noted to. be substantially anhydrous 1 CCl'F .CI-I(OH).CClF

Yield of the anhydrous product was about The above 104l12 C. boilingmixture was soluble with shaking in water. Seperate 104106 C. andIll-112 C. fractions, from mixtures substantially the same as the abovecomposite mixture, were identified by analysis work including infrared,conversion to acetate and urethane, to be respectively CCIF .CH(OH).CCLF.H O and CClF .CH(OH).CClF Other analysis work with respect to theIll-112 C. CF Cl.CH(OH).CClF fraction showed percent F calculated 37.8,found 36.3; percent Cl calculated 33.8 found 35.3: and with regard tothe 104106 C. CClF .CH(OH).CClF .I-I O fraction showed percent Fcalculated 34.7, found 34.7, and percent Cl calculated 32.4, found 32.6

Example 2.-The catalyst employed was commercially available Adamscatalyst, and as initially charged to the reaction was in the form ofthe solid, brown PtO l-E O. About 500 parts of CClF .CO.CClF and fiveparts of the catalyst were charged into a steel autoclave at temperatureinitially about 28 C. Reaction time was about 8 hours, and the reactorwas shaken continuously. Hydrogen was continuously fed into the reactorto main? tain therein a pressure of about 83 lbs. After about 10minutes, temperature in the reactor rose to about 36 C., and maximumtemperature of 38 C. was reached in two hours. The autoclave was ventedafter eight hours thru a Dry Ice-acetone cooled trap, and non-condensedgases were found to contain 0.098 mol of chloride. The liquor in theautoclave was filtered to separate catalyst, and 429 parts of crudeautoclaved product were obtained. This crude material was distilled atsubstantially atmospheric pressure and after removal of a forerun ofabout 55 parts boiling up to about 103104 C., there were obtained about336 parts of condensate boiling substantially in the range of from103104 C. to 112 C., and about 32 parts of still residue boiling aboveabout 112 C. Conversion was about 80%. Analysis work substantially thesame as described in Example 1 showed that the 336 parts of materialboiling substantially in the range of 103-104 to 112 C. was a mixture ofCClF .CH(OH).CClF and its hydrate Yield of the alcohol and hydrate wasabout 67%. The 336 parts of the isopropanol and its hydrate mixture wereredist'illed in the presence of about 150 parts of 96% strength sulfuricacid, and there were obtained as condensate about 310 parts of colorlessliquid boiling in the range of about 111112 C., which material wasidentified by infrared and other analysis as above described to besubstantially anhydrous.

Yield of the anhydrous product was about 77%.

Example 3.The catalyst employed was a fresh quantity of the catalyst ofExample 2. 250 parts of and five parts of catalyst were charged into theautoclave, operation otherwise being substantially the same as inExample 2. On filtration of the liquor in the autoclave, 205 parts ofcrude autoclaved product were obtained. This crude material wasdistilled at substantially atmospheric pressure and after removal of aforerun of about 13 parts boiling up to about 103 C., there wereobtained about 186 parts of condensate boiling substantially in thenange of about 103 C. to Ill-112 C., and about 33 parts of still residueboiling above about 111- 112 C. Conversion was about 95%. Analysis asabove showed that the 186 parts of material boiling substantially in therange of 103 to 111112 C. was a mixture of'CClF .CI-I(OH).CClF and itshydrate Yield of the alcohol and hydrate was about 78%.

Example 4.-A quantity of used, more or less spent and more or less blackcatalytic material from previous runs was dissolved in aqua regia,filtered, and the filtrate evaporation residue was fused at 500520 C.with NaNO The fusion product was cooled, water washed and dried. Fourparts of the thus reconstituted PtO .H O catalyst, and 400 parts of CClF.CO.CClF were charged into the autoclave at temperature of about 30 C.Reaction time was about one hour, temperature rose to about 37 C., andpressure was held at about lbs. Operation otherwise was substantiallythe same as in Example 2. On filtration of the liquor in the autoclave,320 parts of crude autoclaved product were obtained. This crude materialwas distilled at substantially atmospheric pressure and after removal ofa forerun of about 141 parts boiling up to about 103 C., there wereobtained as condensate and still residue and hold up, about 175 parts ofliquid boiling substantially in the range of about 103 C. up to a littleabove 112 C. Conversion was about 64%. Analysis showed that the 175parts of material boiling substantially in the range of 103112 C. was amixture of CCIF CH (OH) .CClF

and its hydrate, CClF .CH(OH).CClF .H O. Yield of the mixture of theisopropanol and its hydrate was about 68%.

In runs such as those of Examples 3 and 4 and other similar runs, ininstances where the isopropanol and its hydrate mixtures wereredistilled in the presence of sulfuric acid as described, yields of theanyhdrous CCIF CH (OH) .CClF

of the order of 60-80% were obtained.

The above described sym-tetrafluorodichloroisopropanol is a notablysatisfactory intermediate for use, e.g. in the manufacture of esterlubricants. To illustrate, the anhydrous alcohol may be reacted withphthalyl chloride to form the phthalate diester of the alcohol,substantially as follows.

Example A.-To 300 g. (1.49 mols) of the above describeddichlorotetrafluoroisopropyl alcohol, 139 g. (0.68 mol) of phthalylchloride were added slowly over a period of about 2 hrs. The mixture wasstirred at room temperature for about 2 hrs., and heated at total refluxfor about 9 /2 hrs. The evolved hydrogen chloride 1.2 mols) wascollected in a water trap. The reaction mixture was poured into icewater, and extracted with ether. The ether extracts were washed withdilute sodium carbonate solution and dried over anhydrous Na SO Ondistillation at pressure in the range of 3-5 mm. there were obtainedabout 200 g. of a crude condensate boiling in the range of about 136-151 C. The crude condensate was redistilled at pressure of about 6 mm.,and there was obtained a substantially pure intermediate fractionamounting to about g., having a boiling point of about 169.5 C./6 mrn.,B.P. corrected, 327.5 C./76O mm. Analysis work, including the following,identified the recovered material as bis-(dichloro-tetrafluoroisopropyl)phthalate.

Analysis: Calculated-C, 31.6; H, 1.14; F, 28.6; CI, 26.7. Found-C, 31.3;H, 1.32; F, 30.8; C1, 26.2.

Comparative Shell four-ball wear tests of the phthalate diesterdemonstrate that wear scar diameters for the diester at 4, 10 and 40 kg.are in the normal range for ester lubricants.

In the appended claims, pressure is given as pounds per square inchgauge, and unless otherwise noted,

is intended to include the anhydrous material and the hydrate.

We claim:

1. The process for making CClF .CH(OH).CClF which comprises subjectingCClF .CO.CClF to the action of hydrogen at temperatures substantially inthe range of 20i00 C. and in the presence'of platinum oxide-platinumblack catalyst in amount substantially in the range of 0.5-3.0% byweight based on the weight of the CClF .CO.CClF charged, and atsuperatmospheric pressure substantially in the range of 60150 lbs.;quantity of hydrogen and reaction time each being high enough to effectsubstantial reaction of CClF .CO.CClF and hydrogen,' ternperature andpressure being correlated to maintain CClF .CO.CClF and'reactionproductsubstantially in liquid phase, and recovering from the resultingreaction mass liquid material boiling substantially in theapproximate'range of 103-113" C. at substantially atmospheric pressure,and containing CClP .CH(OH).CClF

V 2. The process of claim 1 in which the said liquid material isdistilled in the presence of a dehydrating agent and there is recoveredas condensate a liquid boiling at approximately 111-112 C. atsubstantially atmospheric pressure and consisting substantially of 3;The process for making CClF .CH(OH).CClF which comprises subjecting CClF.CO.CClF to the action of hydrogen at temperature substantially in therange of 10100 C. and in the presence of platinum oxide-platinum blackcatalyst in amount substantially in the range of 0.25-5.0% by Weight,based on the Weight of the CClFgCOCClF charged, and at superatmospheric;pressure not substantially above 250 lbs. but at least high enough tomaintain CClF .CO.CClF and reaction product substantially in liquidphase; quantities of hydrogen and catalyst, and temperature and reactiontime each being high enough to effect substantial reaction of andhydrogen to form CClF .CO(OH).CClF

4. The process of claim 3 in which temperature islnot less than about 20C., and temperature and pressure 'substantially in the range of 30250lbs. are correlated so as to maintain CClF .CO.CClF and reaction productsub stantially in liquid phase.

References Cited by the Examiner Swarts: Chem, A bs., vol. 23 (1929),pp. 4440 1,

QdlAS 1.

Smith et al. Ind. and Eng. Chemistry, vol. 49 (1957'), pp. 1241 to 1246(page 1244 relied upon), TP1A58. f

LEON ZITVER, Primary Examiner. CHARLES E. PARKER, Examiner.

1. THE PROCESS FOR MAKING CCLF2CH(OH).CCLF2 WHICH COMPRISES SUBJECTINGCCLF2.CO.CCLF2 TO THE ACTION OF HYDROGEN AT TEMPERATURES SUBSTANITALLYIN THE RANGE OF 20-100*C. AND IN THE PRESENCE OF PLATINUM OXIDE-PLATINUMBLACK CATALYST IN AMOUNT SUBSTANITALLY IN THE RANGE OF 0.5-3.0% BYWEIGHT BASED ON THE WEIGHT OF THE CCLF2.CO.CCLF2 CHARGED, AND ATSUPERATMOSPHERIC PRESSURE SUBSTANTIALLY IN THE RANGE OF 60-150 LBS.;QUANTITY OF HYDROGEN AND REACTION TIME EACH BEING HIGH ENOUGHT TO EFFECTSUBSTANTIAL REACTION OF CCLF2.CO.CCLF2 AND HYDROGEN, TEMPERATURE ANDPRESSURE BEING CORRELATED TO MAINTAIN CCLF2.CO.CCLF2 AND REACTIONPRODUCT SUBSTANTIALLY IN LIQUID PHASE, AND RECOVERING FROM THE RESULTINGREACTION MASS LIQUID MATERIAL BOILING SUBSTANTIALLY IN THE APPROXIMATERANGE OF 103-113*C. AT SUBSTANTIALLY ATMOSPHERIC PRESSURE, ANDCONTAINING CCLF2.CH(OH).CCLF2.